JP2001064133A - Hair dye composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oxidation hair dye composition which gives reduced irritation to the skin, exhibits excellent hair-dyeing effect with fine temporal stability, shows excellent usability and particularly can be prepared as a one pack type. SOLUTION: This hair dye composition is characterized by formulating 0.01-30 wt.% of indoline and/or an indoline derivative (e.g. 5,6-dihydroxyindoline, N- methyl-5,6-dihydroxyindoline or the like) and oxidation enzyme laccase (it is favorable that the enzyme is derived from microorganisms particularly belonging to the genera Myceliophthora and Chytridium). In addition, this composition is capable of including a weak reducing substance, e.g. sodium thiosulfate or the like, in a proportion of 0.01-10 wt.% based on the whole weight of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an indoline and / or
Or a hair dye composition comprising an indoline compound and a laccase, in more detail, less skin irritation, good stability over time, and has an excellent hair dyeing effect, also excellent in usability, especially The present invention relates to an oxidative hair dye composition that can be prepared as a single dosage form.

[0002]

BACKGROUND OF THE INVENTION Generally,
Oxidative hair dye is composed of an oxidation dye (first agent) and an oxidizer (second agent)
These are mixed and reacted at the time of use, and are allowed to act on the head hair to dye gray hair. When a commercially available oxidative hair dye is used, paraphenylenediamine, paraaminophenol, and the like, which are contained in the first agent, are skin sensitizers and may cause rash. On the other hand, almost all of the composition of the second agent uses hydrogen peroxide as an oxidizing agent, and there is a concern that the composition may easily damage hair and skin.

[0003] Therefore, indole compounds and indoline compounds (Japanese Unexamined Patent Publication No.
No. -40857) has been proposed, but at present, hair dyeability is poor with this substance alone. On the other hand, many techniques using an oxidase have been proposed in an attempt to reduce the damage caused by hydrogen peroxide. For example, one using laccase as an oxidase (US Pat. No. 325,174)
No. 2, JP-A-6-172145), those using peroxidase (JP-A-47-10400, JP-A-53-32132) and those using uricase (JP-A-63-246313). Etc. are known. Many of these disclosed technologies are based on the properties of enzymes, such as adding hydrogen peroxide or effectively using hydrogen peroxide to dye hair. Not resolved. Further, laccase also has an unstable property during storage, so that when it is blended into a composition, oxygen in the head space in the container reacts with the oxidation dye, and insoluble aggregates are formed. The generation of such insoluble aggregates in the product is a very problematic hair dye. Therefore, if we do not control this insoluble matter,
There was a big problem that it could not be launched as a product.

[0004] The present invention has been made in view of the above circumstances,
It is an object of the present invention to provide an oxidized hair dye composition having low skin sensitization, good stability over time, an excellent hair dyeing effect, and excellent usability.

[0005]

Means for Solving the Problems and Embodiments of the Invention As a result of intensive studies to achieve the above object, the present inventor has found that the use of indoline and / or an indoline compound together with a laccase provides skin irritation. It has been found that an oxidative hair dye composition which has low durability, has an excellent hair dyeing effect, has excellent stability over time even when prepared in a one-part form, and has excellent usability, is obtained. It has been found that the addition of a weakly reducing substance is more preferable, and the present invention has been accomplished.

Hereinafter, the present invention will be described in more detail. The hair dye composition of the present invention comprises indoline and / or an indoline compound as a color developer and laccase as an oxidizing agent.

Here, indoline and indoline compounds include indoline, 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline,
-Butyl-5,6-dihydroxyindoline, 4-hydroxy-5-methoxyindoline, 6-hydroxy-7
-Methoxyindoline, 6,7-dihydroxyindoline, 4,5-dihydroxyindoline, 4-methoxy-
6-hydroxyindoline, N-hexyl-5,6-dihydroxyindoline, 2-methyl-5,6-dihydroxyindoline, 3-methyl-5,6-dihydroxyindoline, 4-hydroxyindoline, 2,3-dimethyl-5 , 6-Dihydroxyindoline, 2-methyl-5
-Ethyl-6-hydroxyindoline, 2-methyl-5
-Hydroxy-6-β-hydroxyethylindoline,
4-hydroxypropylindoline, 2-hydroxy-
3-methoxyindoline, 6-hydroxy-5-methoxyindoline, 6-hydroxyindoline, 5-hydroxyindoline, 7-hydroxyindoline, 7-aminoindoline, 5-aminoindoline, 4-aminoindoline, 5,6-dihydroxyindoline carboxylic acid,
Examples thereof include 1-methyl-5,6-dihydroxyindoline and salts thereof, and one of these can be used alone or in combination of two or more.

The concentration of the indoline and / or indoline compound used in the present invention varies depending on the frequency of use and the form of the preparation.
01 to 30% (% by weight, the same applies hereinafter), preferably 0.0%
It is preferable to mix 5 to 20%.

In the hair dye composition of the present invention, when a color change is desired, a small amount of an oxidation dye can be used as a coupler. As such an oxidation dye, known dyes can be used. For example, 5-amino-o-cresol described in the quasi-drug raw material standard,
o-aminophenol, m-aminophenol, p-aminophenol, 2,6-diaminopyridine, 5- (2
-Hydroxylethylamino) -2-methylphenol, N, N-bis (β-hydroxyl) -p-phenylenediamine sulfate, p-nitro-o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, N -Phenyl-p-phenylenediamine, resorcinol, 2-hydroxy-5-nitro-2 ', 4'-diaminoazobenzene / sodium sulfate, toluene-2,5-
Diamine, 5-amino-o-cresol / sulfate, p-
Aminophenol / sulfate, o-chloro-p-phenylenediamine / sulfate, 4,4′-diaminodiphenylamine / sulfate, p-methylaminophenol / sulfate,
p-phenylenediamine / sulfate, m-phenylenediamine / sulfate, toluene-2,5-diamine / sulfate,
2,4-diaminophenoxyethanol hydrochloride, toluene-2,5-diamine hydrochloride, m-phenylenediamine hydrochloride, 2,4-diaminophenol hydrochloride,
3,3′-iminodiphenol, p-phenylenediamine hydrochloride, N-phenyl-p-phenylenediamine.
Hydrochloride, N-phenyl-p-phenylenediamine acetate, 1,5-dihydroxynaphthalene, toluene-3,
4-diamine, p-methylaminophenol, N, N '
-Bis (4-aminophenyl) -2,5-diamino-
1,4-quinonediimine, o-aminophenol / sulfate, 2,4-diaminophenol / sulfate, m-aminophenol / sulfate, etc. can be used alone or in an appropriate amount in combination of two or more.

In addition, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 1-amino-4-methylaminoanthraquinone, nitro-p-phenylenediamine, which are often used together with these oxidation dyes. Hydrochloride, 1,4-diaminoanthraquinone, nitro-p-phenylenediamine, picramic acid, sodium piclamate, 2-amino-5-nitrophenol sulfate, resorcinol, nitro-p-phenylenediamine sulfate, p- Direct dyes such as nitro-o-phenylenediamine sulfate and p-nitro-m-phenylenediamine sulfate can also be used.

The concentration of the coupler in the composition may be used only when it is desired to change the hair color, in which case it is 0.001 to 5%, preferably 0.001%.
It is better to mix 5 to 2%.

Here, in the case of the present invention, for example, WO99 /
36034, WO99 / 36035, WO99 / 360
36, WO 99/36037, WO 99/36038,
WO99 / 36039, WO99 / 36040, WO9
9/36041, WO99 / 36042, WO99 / 3
6043, WO99 / 36044, WO99 / 3604
5, and various dyes (developed substances or oxidizable base compounds) and coupling compounds (coupling agents) described in WO 99/36046 can be used.

The oxidizing base compound includes, for example, para-phenylenediamines, double basic compounds, para-
Examples thereof include aminophenols, ortho-aminophenols, and heterocyclic oxidizable base compounds.

The para-phenylenediamines suitable as the oxidizing base compound which can be added to the hair dye composition of the present invention include a compound represented by the following general formula (1) and an acid salt adduct thereof. it can.

[0015]

Embedded image

In the above formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monohydroxyalkyl group having 1 to 4 carbon atoms, a polyhydroxyalkyl group having 2 to 4 carbon atoms, C1-4) alkoxy (C1-4) alkyl group having a carbon alkyl group having 1 to 4 carbon atoms which is substituted by a group containing a nitrogen, a phenyl group or a 4'-aminophenyl radical, R ² is hydrogen An atom, an alkyl group having 1 to 4 carbon atoms,
A monohydroxyalkyl group having 1 to 4 carbon atoms, 2 to 2 carbon atoms
4 polyhydroxyalkyl radical, an alkyl group having 1 to 4 carbon atoms which is substituted by a group containing an alkoxy (1-4 carbon atoms) alkyl group, a nitrogen (1 to 4 carbon atoms), R ³ is a hydrogen atom A halogen atom such as chlorine, bromine, iodine or fluorine, an alkyl group having 1 to 4 carbon atoms,
A monohydroxyalkyl group, a hydroxyalkoxy group having 1 to 4 carbon atoms, an acetylaminoalkoxy group having 1 to 4 carbon atoms, a mesylaminoalkoxy group having 1 to 4 carbon atoms or a carbamoylaminoalkoxy group having 1 to 4 carbon atoms. And R ⁴ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

Among the nitrogen-containing groups in the above formula (1), amino groups, mono (1-4 carbon) alkylamino groups, di (1-4 carbon) alkylamino groups, and tri (1-4 carbon) alkylamino groups 4) Alkylamino groups, monohydroxy (C1-4) alkylamino groups, imidazolinium and ammonium are particularly preferred.

Among the para-phenylenediamines represented by the above formula (1), the following para-phenylenediamines are more particularly preferred. That is, para-phenylenediamine, para-toluenediamine, 2-chloropara-phenylenediamine, 2,3-dimethylpara-phenylenediamine, 2,6-dimethylpara-phenylenediamine, 2,6-diethylpara-phenylenediamine, 2, 5-dimethylpara-phenylenediamine, N,
N-dimethylpara-phenylenediamine, N, N-diethylpara-phenylenediamine, N, N-dipropylpara-phenylenediamine, 4-aminoN, N-diethyl-3-methylaniline, N, N-bis (β-hydroxy-
Ethyl) para-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino 2-methylaniline,
4-N, N-bis (β-hydroxyethyl) amino 2-
Chloroaniline, 2-β-hydroxyethyl para-phenylenediamine, 2-fluoropara-phenylenediamine, 2-isopropylpara-phenylenediamine, N-
(Β-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl para-phenylenediamine,
N, N-dimethyl-3-methylpara-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) para-
Phenylenediamine, N- (β, γ-dihydroxypropyl) para-phenylenediamine, N- (4′-aminophenyl) para-phenylenediamine, N-phenylpara-phenylene-diamine, 2-β-hydroxyethyloxypara- Phenylenediamine, 2-β-acetylaminoethyloxypara-phenylenediamine, N- (β-methoxyethyl) para-phenylenediamine and its acid salt adducts.

Among the para-phenylenediamines represented by the above formula (1), the following are particularly preferred. Para
Phenylenediamine, paratoluylenediamine, 2-isopropylpara-phenylenediamine, 2-β-hydroxyethylpara-phenylenediamine, 2-β-hydroxyethyloxypara-phenylenediamine, 2,6-dimethylpara-phenylenediamine, 2 , 6-Diethylpara-phenylenediamine, 2,3-dimethylpara-phenylenediamine, N, N-bis (β-hydroxyethyl) para-phenylenediamine, 2-chloropara-phenylenediamine, 2-β-acetylaminoethyloxypara -Phenylenediamine and its acid salt adducts.

In the present invention, the double basic compound is a crosslinkable group having an amino group and / or a hydroxyl group.
A compound is meant that contains at least two aromatic nuclei.

As the oxidizable base compound which can be incorporated in the hair dye composition of the present invention, a compound represented by the following general formula (2) and an acid salt adduct thereof are preferred among the double basic compounds. .

[0022]

Embedded image

In the above formula, Z ¹ and Z ² may be the same or different and each represents a hydroxyl group or a —NH ₂ group, and has an alkyl group having 1 to 4 carbon atoms or a bridging group Y. May be substituted. The bridging radical Y is a straight-chain or branched alkylene chain having from 1 to 14 carbon atoms, a group containing one or more nitrogen atoms and / or one or more heterogeneous groups such as oxygen, sulfur or nitrogen. It can be interrupted or terminated by an atom, and can be optionally substituted with a plurality of hydroxyl groups or alkyl groups having 1 to 6 carbon atoms.

R ⁵ and R ^{6 each} represent hydrogen or a halogen atom, an alkyl group having 1 to 4 carbon atoms, a monohydroxyalkyl group having 1 to 4 carbon atoms, a polyhydroxyalkyl group having 1 to 4 carbon atoms, 4 represents an aminoalkyl group or a bridging group Y, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R
¹² may be the same or different and represent a hydrogen atom,
Represents a crosslinking group Y or an alkyl group having 1 to 4 carbon atoms.

Accordingly, the compound represented by the general formula (2) contains a single crosslinking group Y per molecule.

Among the nitrogen-containing groups represented by the general formula (2), the following groups can be exemplified. Amino group,
Mono (C 1-4 alkylamino group, di (C 1
-4) alkyl-amino group, tri (1-4 carbon) alkylamino group, monohydroxy (1-4 carbon) alkylamino group, imidazolinium and ammonium.

As the double basic compound represented by the general formula (2), more specifically, for example, N, N = bis-
(Β-hydroxyethyl) N, N′-bis- (4′-aminophenyl) 1,3 diaminopropanol, N, N =
Bis- (β-hydroxyethyl) N, N = bis- (4 ′
-Aminophenyl) ethylenediamine, N, N = bis-
(4′-aminophenyl) tetramethylenediamine,
N, N'-bis- (β-hydroxyethyl) N, N'-
Bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl)
N, N'-bis- (4'-amino, 3-methylphenyl) ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane and its acid salt adducts Can be.

Among the compounds represented by the above general formula (2), particularly preferred double basic compounds include N, N-
Bis- (β-hydroxyethyl) N, N′-bis-
(4′-aminophenyl) 1,3 diaminopropanol, 1,8-bis (2,5-diaminophenoxy)-
3,5-dioxaoctane and its acid salt adducts can be mentioned.

The para-aminophenols, which are oxidizable base compounds that can be added to the hair dye composition of the present invention, include:
In particular, compounds represented by the following general formula (3) and those obtained by adding a base to them with an acid are preferred.

[0030]

Embedded image

In the above formula, R ¹³ is a hydrogen atom or a halogen atom, an alkyl group having 1 to 4 carbon atoms, a monohydroxyalkyl group having 1 to 4 carbon atoms, (C 1 to C 4)
Alkoxy (C 1-4) alkyl group, C 1-4
Represents an aminoalkyl group or a (C1-4) hydroxyalkyl (C1-4) aminoalkyl group,
R ¹⁴ is a hydrogen atom or a halogen atom, having 1 to 4 carbon atoms.
An alkyl group, a monohydroxyalkyl group having 1 to 4 carbon atoms, a polyhydroxyalkyl group having 2 to 4 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, a cyanoalkyl group having 1 to 4 carbon atoms, or (1 carbon atoms) ~ 4) alkoxy (1 carbon atom)
-4) represents an alkyl group. Therefore, at least one of R ^{13 and} R ¹⁴ represents a hydrogen atom.

As the para-aminophenols represented by the general formula (3), more specifically, for example, para-aminophenol, 4-amino-3-methylphenol,
-Amino 3-fluorophenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4
-Amino 2-methoxymethylphenol, 4-amino-2
-Aminomethylphenol, 4-amino2-([beta] -hydroxyethylaminomethyl) phenol, 4-amino2-fluorophenol and their acid salt adducts.

The ortho-aminophenols which are oxidizable base compounds which can be added to the hair dye composition of the present invention include, for example, 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol , 5-
Acetamide 2-aminophenol and its acid salt adducts can be mentioned.

As the oxidizable base compound which can be added to the hair dye composition of the present invention, pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, pyrazolo-pyrimidine derivatives and their acid salt adducts are suitable.

Examples of the pyridine derivative include, for example, Patent GB-PS1026978 and GB-PS115319.
6, the compound described in 6, ie, 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine, 2,3-diamino6-methoxypyridine, 2-
(Β-methoxyethyl) amino 3-amino 6-methoxypyridine, 3,4-diaminopyridine and their salt adducts are preferred.

Examples of the pyrimidine derivative include, for example, German Patent DE2359399 or Japanese Patent JP8
8-169571 and JP91-333495 or in patent application WO 96/15765. That is,
2,4,5,6-tetra-aminopyrimidine, 4-hydroxy2,5,6-triaminopyrimidine, 2-hydroxy4,5,6-triaminopyrimidine, 2,4-dihydroxy5,6-diaminopyrimidine , 2,5,6-triaminopyrimidine and those obtained by adding a base thereto with an acid are preferred.

Examples of the pyrazole derivative include, for example, patents DE38443892 and DE4133397, and patent applications WO94 / 08969 and WO94 / 0897.
0, FR-A2733 and DE19543988. That is, 4,5-diamino 1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino1
-(4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino3
-Methyl 1-phenylpyrazole, 4,5-diamino 1
-Methyl 3-phenylpyrazole, 4-amino 1,3-
Dimethyl 5-hydrazinopyrazole, 1-benzyl 4,
5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl 1-methylpyrazole, 4,5-diamino-1-terttobutyl 3-methylpyrazole, 4,
5-diamino 1- (β-hydroxyethyl) 3-methylpyrazole, 4,5-diamino1-ethyl 3-methylpyrazole, 4,5-diamino1-ethyl 3- (4′-methoxyphenyl) pyrazole, 5-diamino 1-ethyl 3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl 1-methylpyrazole, 4,5
-Diamino-3-hydroxymethyl 1-isopropylpyrazole, 4,5-diamino-3-methyl1-isopropylpyrazole, 4-amino5- (2'-aminoethyl) amino1,3-dimethylpyrazole, 3,4,5- Triaminopyrazole, 1-methyl 3,4,5-triaminopyrazole, 3,5-diamino 1-methyl 4-methylaminopyrazole, 3,5-diamino-4- (β-hydroxyethyl) amino 1-methylpyrazole and Examples thereof include acid salt adducts thereof.

The above pyrazolopyrimidine derivatives include:
For example, pyrazolo- [1,5-a] -pyrimidine-3,7-
Diamine, 2-methylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,5-dimethylpyrazolo-
[1,5-a] -pyrimidine-3,7-diamine, pyrazolo- [1,5-a] -pyrimidine-3,5-diamine,
2,7-dimethylpyrazolo- [1,5-a] -pyrimidine-3,5-diamine, 3-aminopyrazolo- [1,5-
a] -Pyrimidin-7-ol, 3-amino-5-methylpyrazolo- [1,5-a] -pyrimidin-7-ol, 3-
Aminopyrazolo- [1,5-a] -pyrimidin-5-ol, 2- (3-aminopyrazolo- [1,5-a] -pyrimidin-7-ylamino) -ethanol, 3-amino7-
Hydroxyethylamino-5-methyl-pyrazolo-
[1,5-a] -pyrimidine, 2- (7-aminopyrazolo- [1,5-a] -pyrimidin-3-ylamino) -ethanol, 2-[(3-aminopyrazolo- [1,5-a]-
Pyrimidin-7-yl)-(2-hydroxyethyl)-
Amino] -ethanol, 2-[(7-amino-pyrazolo-
[1,5-a] -Pyrimidin-3-yl)-(2-hydroxyethyl) -amino] -ethanol, 5,6-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine , 2,6-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,5, N-7, N-7-
Tetramethylpyrazolo- [1,5-a] -pyrimidine-
Examples include 3,7-diamine and their salt adducts and their tautomeric forms when there is a compatible equilibrium.

The above pyrazolopyrimidine derivatives include:
For example, pyrazolo [1,5-
a] Pyrimidines, their acidic or basic salt adducts and their tautomeric forms when there is a tautomeric equilibrium.

[0040]

Embedded image

In the above formula, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be the same or different and include a hydrogen atom,
An alkyl group having 1 to 4 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 4 carbon atoms, a polyhydroxyalkyl group having 2 to 4 carbon atoms, (1 to 4 carbon atoms) alkoxy (1 to 4 carbon atoms)
4) an alkyl group, an aminoalkyl group having 1 to 4 carbon atoms (the amine is protected by an acetyl group, a ureido group or a sulfonyl group), an alkylamino (1 to 4 carbon atoms) alkyl group (1 to 4 carbon atoms) , Di [(1-4 carbon atoms) alkyl] amino (1-4 carbon atoms) alkyl group (a dialkyl group can form a carbon ring, a 5-membered ring or a 6-membered ring), hydroxy (1-4 carbon atoms) 4) represents an alkyl group or di [hydroxy (1-4 carbon) alkyl] amino (1-4 carbon) alkyl group.

X groups which may be the same or different are
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 4 carbon atoms, a polyhydroxyalkyl group having 2 to 4 carbon atoms, an amino (1 to 4 carbon atoms) alkyl group, To 4) alkyl (1 to 4 carbon atoms) aminoalkyl group, di [(1 to 4 carbon atoms) alkyl] amino (1 to 4 carbon atoms) alkyl group (the dialkyl group is a carbon ring, a 5-membered ring or a 6-membered ring) Can be formed), a hydroxy (C 1-4 alkyl) group or a di [hydroxy (C 1-4 alkyl) amino] (C 1-4
4) alkyl group or di [(C 1-4 alkyl)]
It represents an amino group, a halogen atom, a carboxylic acid group or a sulfonic acid group.

I is 0, 1, 2, or 3, and p is 0
Or 1, q is 0 or 1, n is 0 or 1, and the total p + q is not 0, p + q
Is 2, n has the value 0, and the NR ¹⁵ R ¹⁶ and NR ¹⁷ R ¹⁸ groups are (2,3); (5,6); (6,7);
Occupies (3,5) or (3,7). On the other hand, when p + q is 1, n has a value of 1 and NR ¹⁵
R ¹⁶ group (or NR ¹⁷ R ¹⁸ group) and hydroxyl group are (2,
(3); occupy (5, 6); (6, 7); (3, 5) or (3, 7).

Pyrazolo represented by the above general formula (4)
If [1,5-a] -pyrimidine contains a hydroxyl group at one of the 2,5 or 7 positions at the α-position to the nitrogen atom, a compatible equilibrium exists, for example the reaction It can be shown by an equation.

[0045]

Embedded image

Pyrazolo represented by the above general formula (4)
[1,5-a] -pyrimidine includes, for example, pyrazolo-
[1,5-a] -pyrimidine-3,7-diamine, 2,5
-Dimethylpyrazolo- [1,5-a] -pyrimidine-3,
7-diamine, pyrazolo- [1,5-a] -pyrimidine-
3,5-diamine, 2,7-dimethylpyrazolo- [1,
5-a] -pyrimidine-3,5-diamine, 3-aminopyrazolo- [1,5-a] -pyrimidin-7-ol, 3-
Aminopyrazolo- [1,5-a] -pyrimidin-5-ol, 2- (3-aminopyrazolo- [1,5-a] -pyrimidin-7-ylamino) -ethanol, 2- (7-aminopyrazolo- [1,5 -A] -pyrimidin-3-ylamino)
-Ethanol, 2-[(3-aminopyrazolo- [1,5-
a] -Pyrimidin-7-yl)-(2-hydroxy-ethyl) -amino] ethanol, 2-[(7-aminopyrazolo- [1,5-a] -pyrimidin-3-yl)-(2-hydroxy-ethyl) -Amino] ethanol, 5,6-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7 -Diamine, 2,5-N7, N7-tetramethylpyrazolo- [1,5-a] -pyrimidine-3,7
-Diamines and their salt adducts, and when there is a compatible equilibrium, examples thereof include compatible isomers.

The pyrazolo represented by the above general formula (4)
[1,5-a] -Pyrimidines can be made by cyclization of aminopyrazoles based on the synthetic methods described in the following references. (1) EP 628559 BEIERSDORF-L
ILLY (2) R.I. Vishdu, H .; Navedul, Ind
ian J. Chem. , 34b (6), 514, 19
95. (3) N.P. S. Ibrahim, K .; U. Sadek,
F. A. Abdel-Al, Arch. Pharm. ,
320, 240, 1987. (4) R.I. H. Springer, M .; B. Schol
ten, D .; E. FIG. O'Brien, T .; Novinso
n, J .; P. Miller, R.A. K. Robins,
J. Med. Chem. , 25, 235, 1982. (5) T. Novinson, R .; K. Robins,
T. R. Matthews, J .; Med. Chem. ,
20, 296, 1977. (6) US 3907799 ICN PHARMAC
EUTICAL

The pyrazolo- [1,5-a]-of the above formula (4)
Pyrimidines can be further made by cyclization of hydrazine based on synthetic methods described in the following references. (1) A. McKillop, R.A. J. Kobilec
ki, Heterocycles, 6 (9), 135
5,1977. (2) E. Alcade, J. et al. De Mendoza,
J. M. Marcia-Marquina, C.I. Alm
era, J .; Elguero, J .; Heterocyc
lic Chem. , 11 (3), 423, 1974. (3) K. Saito, I .; Hori, M .; Higar
ashi, H .; Midorikawa, Bull. Ch
em. Soc. Japan, 47 (2), 476, 19
74.

Examples of the pyrazole derivative include, for example, patents or patent applications DE3848392, DE4133.
957, DE 4234886, DE 4234887, F
R2733749, FR2735365, WO94 / 0
8969 and WO 94/08970 are also mentioned therein, for example 4,5-diaminopyrazole, 4,5
-Diamino-1-methylpyrazole, 1-benzyl 4,
5-diaminopyrazole, 3,4-diaminopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4-amino1,3-dimethyl5-hydrazinopyrazole, 4,5-diamino-3-methyl1- Phenyl pyrazole, 4,5-diamino 3-methyl 1-tert-butyl pyrazole, 4,5-diamino 1-methyl 3-tert-butyl pyrazole, 4,5-diamino 1-ethyl 3-
Methylpyrazole, 4,5-diamino 1-ethyl 3-
(4′-methoxyphenyl) pyrazole, 4,5-diamino 1-ethyl 3-hydroxymethylpyrazole, 4,
Compounds such as 5-diamino-3-hydroxymethyl 1-methylpyrazole, 4,5-diamino-3-hydroxymethyl 1-isopropylpyrazole, 4,5-diamino-3-methyl1-isopropylpyrazole and their acid salt adducts are exemplified. be able to.

The oxidizing basic compound or the basic compound is used in an amount of about 0.0005 to about 12%, preferably 0.005 to 6%, based on the total weight of the hair dye composition of the present invention. .

Meta-aminophenols or meta-aminophenols (plurality) suitable as a coupling agent that can be added to the hair dye composition of the present invention include a compound represented by the following general formula (5) and an acid thereof. It is preferred to select from salt adducts.

[0052]

Embedded image

In the above formula, R ¹⁹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monohydroxyalkyl group having 1 to 4 carbon atoms or a polyhydroxyalkyl group having 2 to 6 carbon atoms. ²⁰ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom selected from chlorine, bromine and fluorine, and R ²¹ represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. An alkoxy group having 1 to 4 carbon atoms, a monohydroxyalkyl group having 1 to 4 carbon atoms, a polyhydroxyalkyl group having 2 to 4 carbon atoms, a monohydroxyalkoxy group having 1 to 4 carbon atoms or 2 carbon atoms
Represents 4 to 4 polyhydroxyalkoxy groups.

Among the meta-aminophenols represented by the general formula (5), meta-aminophenol, 5-
Amino-2-methoxyphenol, 5-amino-2-
(Β-hydroxyethyloxy) -phenol, 5-amino-2-methylphenol, 5-N- (β-hydroxyethyl) -amino-2-methylphenol, 5-N-
(Β-hydroxyethyl) -amino-4-methoxy-2
-Methylphenol, 5-amino-4-methoxy-2-
Methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-2,4-dimethoxyphenol, 5- (γ-hydroxypropylamino) -2-methylphenol and their acid salt adducts, etc. Particularly preferred.

As meta-phenylenediamines or meta-phenylenediamines (plurality) suitable as a coupling agent in the hair dye composition of the present invention, a compound represented by the following general formula (6) and an acid salt thereof are added. Things are preferred.

[0056]

Embedded image

In the above formula, R ²² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monohydroxyalkyl group having 1 to 4 carbon atoms or a polyhydroxyalkyl group having 2 to 6 carbon atoms. ²³ and R ²⁴ may be the same or different and are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monohydroxyalkoxy group having 1 to 4 carbon atoms or a polyhydroxyalkoxy group having 2 to 6 carbon atoms. the stands, R ²⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, aminoalkoxy group having 1 to 4 carbon atoms, monohydroxyalkyl alkoxy group having 1 to 4 carbon atoms, or polyhydroxy alkoxy group having 2 to 4 carbon atoms Represents a 2,4-diaminophenoxyalkoxy group.

Among the meta-phenylenediamines represented by the general formula (6), 2,4-diaminobenzene,
3,5-diamino-1-ethyl-2-methoxybenzene, 3,5-diamino-2-methoxy-1-methylbenzene, 2,4-diamino-1-ethoxybenzene, 1,
3-bis (2,4-diaminophenoxy) propane, bis (2,4-diaminophen-oxy) -methane, 1-
(Β-aminoethyloxy) -2,4-diamino-benzene, 2-amino-1- (β-hydroxy-ethyloxy)
-4-methylamino-benzene, 2,4-diamino-1
-Ethoxy 5-methyl-benzene, 2,4-diamino-
5- (β-hydroxyethyloxy) -1-methylbenzene, 2,4-diamino-1- (β, γ-dihydroxy-
Propoxy) benzene, 2,4-diamino-1- (β
-Hydroxyethyloxy) -benzene, 2-amino-4
—N- (β-hydroxyethyl) -amino-1-methoxy-benzene and their acid salt adducts are particularly preferred.

The meta-diphenols or meta-diphenols (plural) which can be used as a coupling agent in the hair dye composition of the present invention are compounds represented by the following general formula (7) and addition of an acid salt thereof. Things are preferred.

[0060]

Embedded image

In the above formula, R ²⁶ and R ²⁷ may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen selected from chlorine, bromine and fluorine. Represents an atom.

Among the meta-diphenols represented by the general formula (7), 1,3-dihydroxy-benzene,
2-methyl-1,3-dihydroxy-benzene, 4-chloro-1,3-dihydroxy-benzene, 2-chloro-
1,3-Dihydroxybenzene and their acid salt adducts are particularly preferred.

The hair dye composition of the present invention may further comprise a coupling agent different from the above-mentioned coupling agent alone or two.
More than one species can be combined as appropriate,
In particular, it is also possible to mix direct dyes which improve the color or enhance the gloss of the dyes alone or in combination of two or more.

Examples of the heterocyclic coupling agent which can be incorporated in the hair dye composition of the present invention include benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, pyrazolo-azole derivatives, pyrrolo-azole derivatives, imidazolo-azole derivatives, pyrazolo -Pyrimidine derivatives, pyrazoline 3,5-dione derivatives, pyrrolo- [3,2-d]
Oxazole derivatives, pyrazolo- [3,4-d] thiazole derivatives, thiazolo-azole S oxide derivatives, thiazolo-azole S, S dioxide derivatives and their acid salt adducts are preferred.

As the benzimidazole derivative which can be added as a heterocyclic coupling agent to the hair dye composition of the present invention, a compound represented by the following formula (I) and an acid salt adduct thereof are preferable.

[0066]

Embedded image

In the above formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ represents a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms or a phenyl group,
R ₃ represents a hydroxyl group, an amino group or a methoxy group, and R ₄ represents a hydrogen atom, a hydroxyl group, a methoxy group or an alkyl group having 1 to 4 carbon atoms. And R ₃
And R ₄ is, if R ₃ is an amino group, it is in position 4;
If R ₃ is in position ₄ , R ₄ is in position 7; if R ₃ is in position 5, R ₄ is in position 6.

Among the benzimidazole derivatives represented by the above general formula (I), 4-hydroxybenzimidazole, 4-aminobenzimidazole, 4-hydroxy-7
-Methylbenzimidazole, 4-hydroxy-2-methylbenzimidazole, 1-butyl-4-hydroxybenzimidazole, 4-amino-2-methylbenzimidazole, 5,6-dihydroxybenzimidazole, 5- Hydroxy-6-methoxybenzimidazole, 4,7-dihydroxybenzimidazole, 4,7-dihydroxy-1
-Methylbenzimidazole, 4,7-dimethoxybenzimidazole, 5,6-dihydroxy-1-methylbenzimidazole, 5,6-dihydroxy-2-methylbenzimidazole, 5,6-dimethoxybenzimidazole and Those acid salt adducts are particularly preferred.

As the benzomorpholine derivative which can be added as a heterocyclic coupling agent to the hair dye composition of the present invention, a compound represented by the following formula (II) and an acid salt adduct thereof are particularly preferable.

[0070]

Embedded image

In the above formula, R ₅ and R ₆ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z represents a hydroxyl group or an amino group. Represent.

Among the benzomorpholine derivatives represented by the above general formula (II), 6-hydroxy-1,4-benzomorpholine, N-methyl 6-hydroxy-1,4-benzomorpholine, 6-amino 1, 4-Benzomorpholine and their acid salt adducts are particularly preferred.

Among the sesamol derivatives which can be added as a heterocyclic coupling agent to the hair dye composition of the present invention, the compounds represented by the following formula (III) and the acid salt adduct thereof are particularly preferred.

[0074]

Embedded image

In the above formula, R ₇ is a hydroxyl group, an amino group, an alkylamino group having 1 to 4 carbon atoms, a monohydroxyalkylamino group having 1 to 4 carbon atoms or a polyhydroxyalkyl group having 2 to 4 carbon atoms. Represents an alkylamino group,
R ₈ represents a hydrogen atom, a halogen atom or a carbon number of 1 to 4
Represents an alkoxy group.

Among the sesamol derivatives represented by the general formula (III), 2-bromo-4,5-methylenedioxyphenol, 2-methoxy4,5-methylenedioxyaniline, 2- (β-hydroxyethyl) Amino 4,5
Methylenedioxybenzene and their acid salt adducts are particularly preferred.

The pyrazolo-azole derivatives which can be incorporated as a heterocyclic coupling agent into the hair dye composition of the present invention include the following publications: Chem. Ber. 32,7
97, (1899), Chem. Ber. 89,255
0, (1956); Chem. Soc. Perki
n trans I, 2047, (1977); P
rakt. Chem. , 320, 533, (1978).
Patents and patent applications similar to: FR 2 075 583
EP-A-119 860, EP-A-285274,
EP-A-244 160, EP-A-578 24
8, GB 1458 377, US 3 277 55
4, US3 419 391, US3 061 43
2, US4500630, US37250
67, US 3 926 631, US 5 457
210, JP 84/99437, JP 83/420
45, JP 84/162548, JP 84/171
956, JP 85/33552, JP 85/436
59, JP 85/172998, JP 85/190
Compounds such as those described in 779 can be used particularly preferably.

More specifically, as the pyrazolo-azole derivative, for example, 2-methylpyrazolo [1,5-b]
-1,2,4-triazole, 2-ethylpyrazolo
[1,5-b] -1,2,4-triazole, 2-isopropylpyrazolo [1,5-b] -1,2,4-triazole, 2-phenylpyrazolo [1,5-b]- 1,2,4-
Triazole, 2,6-dimethylpyrazolo [1,5-b]
-1,2,4-triazole, 7-chloro2,6-dimethylpyrazolo [1,5-b] -1,2,4-triazole, 3,6-dimethyl-pyrazolo [3,2-c]- 1,
2,4-triazole, 6-phenyl-3-methylthio-pyrazolo [3,2-c] -1,2,4-triazole,
Examples thereof include 6-aminopyrazolo [1,5-a] benzimidazole and their acid salt adducts.

The pyrrolo-azole derivatives which can be incorporated as a heterocyclic coupling agent into the hair dye composition of the present invention include the following patents and patent applications: US Pat.
No. 56526, EP-A-557 851, EP-A-
578 248, EP-A-518 238, EP-A
-456 226, EP-A-488 909, EP-
A-488 248 and publications such as: R.
LiljegrenBer. 1964, 3436;
J. Browne, J.M. C. S. , 1962, 514
9; Magnus, J .; A. C. S. , 1990,
112, 2465; Magnus, J .; A. C.
S. Angew., 1987, 109, 2711; Ch
em. 1960, 72, 956; and Rec. Tra
v. Chim. 1961, 80, 1075.

As the above pyrroloazole derivative, more specifically, 5-cyano-4-ethoxycarbonyl-8-
Methylpyrrolo [1,2-b] -1,2,4-triazole, 5-cyano-8-methyl-4-phenylpyrrolo
[1,2-b] -1,2,4-triazole, 7-amino-6-ethoxycarbonylpyrrolo [1,2-a] -benzimidazole and their acid salt adducts.

The imidazolo-azole derivatives which can be added as a heterocyclic coupling agent to the hair dye composition of the present invention include those described in US Pat.
Compounds described in JP-A-279337, JP-A-6-236011 and JP-A-7-92632 can be exemplified.

As the above imidazolo-azole derivative,
More specifically, 7,8-dicyano-imidazolo [3,
2-a] -imidazole, 7,8-dicyano-4-methyl-imidazolo [3,2-a] -imidazole and their acid salt adducts.

Examples of the pyrazolo-pyrimidine derivative which can be added to the hair dye composition of the present invention as a heterocyclic coupling agent include the compounds described in EP-A-304-001.

As the pyrazolo-pyrimidine derivative,
More specifically, pyrazolo- [1,5-a] -pyrimidin-7-one, 2,5-dimethylpyrazolo- [1,5-a]
-Pyrimidin-7-one, 2-methyl-6-ethoxycarbonylpyrazolo- [1,5-a] -pyrimidin-7-one, 2-methyl-5-methoxymethylpyrazolo- [1,
5-a] -pyrimidin-7-one, 2-tert-butyl-5-trifluoromethylpyrazolo- [1,5-a] -pyrimidin-7-one, 2,7-dimethylpyrazolo- [1,
5-a] -pyrimidin-5-one and their acid salt adducts.

As the pyrazoline-3,5-dione derivative which can be compounded as a heterocyclic coupling agent in the hair dye composition of the present invention, the following patents and patent applications:
Compounds described in JP-A-36159, JP-A-7-84348, U.S. Pat. No. 4,128,425 and the following publications can be mentioned. (1) L. WYZGOWSKA, Acta. Pol. P
harm. 1982, 39 (1-3), 83. (2) E. HANNIG, Pharmazie, 198
0, 35 (4), 231 (3) M.P. H. ELNAGDI, Bull. Chem.
Soc. Jap. , 46 (6), 1830, 1973 (4) G.I. CARDILLO, Gazz. Chim. I
tal. 1966, 96, (8-9), 973

As the pyrazoline-3,5-dione derivative, more specifically, 1,2-diphenylpyrazolin-3,5-dione, 1,2-diethylpyrazolin-3,
5-dione and their acid salt adducts.

As the pyrrolo- [3,2-d] -oxazole derivative which can be added as a heterocyclic coupling agent to the hair dye composition of the present invention, the compounds described in JP-A-7-325375 can be mentioned. be able to.

Examples of the pyrazolo- [3,4-d] -thiazole derivative which can be added as a heterocyclic coupling agent to the hair dye composition of the present invention include JP-A-7-244361 and J. Pharm. Heterocycl. Chem. 16, 13,
(1979).

The thiazolo-azole S-oxide derivatives and thiazolo-azole S, S-dioxide derivatives which can be incorporated as a heterocyclic coupling agent into the hair dye composition of the present invention are described in the following documents. Compounds can be mentioned. (1) JP-A-7-98489; (2) Khim. Geterotsilk. Soedi
n, 1967, p. 93; Prakt. Chem. , 318, 197
6, p. 12; (4) Indian J .; Heterocycl. Ch
em. 1995, 5 (2), p. 135; (5) Acta. Pol. Pharm. 1995, 52
(5), 415; (6) Heterocycl. Commun. 199
5, 1 (4), 297; (7) Arch. Pharm. (Weinheim, G
er. ), 1994, 327 (12), 825.

The above-mentioned heterocyclic oxidation dye, that is, the heterocyclic oxidizing base compound and / or the heterocyclic coupling agent is
It is preferably about 0.0001 to about 12%, particularly preferably about 0.005 to 6%, based on the total weight of the hair dye composition of the present invention.

The hair dye composition of the present invention further comprises at least one oxidizing base compound in the form of a benzene compound and at least one coupling agent in the form of a benzene compound, in addition to the above heterocyclic oxidation dye. And / or at least one direct dye which improves color and enhances gloss.

Coupling agents suitably incorporated in the hair dye composition of the present invention are those conventionally used in oxidative hair dye compositions, such as metaphenylenediamines and metaaminophenol. , Metadiphenols, heterocyclic coupling agents and acid salt adducts.

As such coupling agents, more specifically, for example, 2-methyl-5-amino-phenol, 5-N- (β-hydroxyethyl) -amino-2-
Methyl-phenol, 3-amino-phenol, 1,3
-Dihydroxybenzene, 1,3-dihydroxy-2-
Methyl-benzene, 4-chloro-1,3-dihydroxy-benzene, 2,4-diamino-1- (β-hydroxyethyloxy) -benzene, 2-amino-4- (β-hydroxyethylamino) -1- Methoxy-benzene, 1,
3-diamino-benzene, 1,3-bis- (2,4-diaminophenoxy) -propane, sesamol, α-naphthol, 6-hydroxy-indole, 4-hydroxy-indole, 4-hydroxy-N-methyl-indole , 6-hydroxy-indoline, 2,6-dihydroxy-4-methyl-pyridine, 1-H-3-methyl-pyrazol-5-one, 1-phenyl-3-methyl-pyrazol-5-one, 2,6 -Dimethyl-pyrazole-
[1,5b] -1,2,4-triazole, 2,6-dimethyl- [3,2-c] -1,2,4-triazole, 6-
Methyl-pyrazolo [1,5-a] -benzimidazole and their acid salt adducts can be mentioned.

In addition, as a coupling agent, 2
-Amino-3-hydroxypyridine can also be used.

It is preferable that such a coupling agent weighs about 0.0001 to about 10%, particularly about 0.005 to about 5%, based on the whole hair dye composition of the present invention.

Examples of the cationic direct dye which can be incorporated in the hair dye composition of the present invention include a cationic amino-anthraquinone dye, a cationic mono- or di-azo dye and a cationic naphthoquinone dye. Can be.

In the above example, particularly, [8-[(p-aminophenyl) azo] -7-hydroxy-2-naphthyl] trimethylammonium hydrochloride (also referred to as Basic Brown 16 or Arianol Mahogany 306002 in terms of pigment index) ), 3-[(4-amino-6-bromo-
5,8-dihydro-1-hydroxy-8-imino-5
[Oxo-2-naphthalenyl) amino] N, N, N-trimethyl-benzeneaminium hydrochloride (Dye index: Basic Blue 99 or Alianol Steel Blue 30
6004), 7-hydroxy-8-
[(2-methoxyphenyl) azo] -N, N, N-trimethyl-2-naphthalene aminium hydrochloride (also referred to as Basic Red 76 or Arianol Mader Red in the dye index), [8- (4-amino- 2-nitrophenyl) azo] -7-hydroxy-2-naphthyl] trimethylammonium hydrochloride (Dye index: Basic Brown 17 or Arianol Sienna Brown 30600)
1) and 3-[(4,5-dihydro-
3-Methyl-5-oxo-1-phenyl-1H-pyrazol-4-yl) azo] N, N, N-trimethylbenzaminium hydrochloride (Dye index is also called Basic Yellow 57 or Alianol Straw Yellow 306005) Is preferred.

The cationic dye can be further selected from the following.

[0099]

Embedded image

Here, in the above formula, D represents a nitrogen atom or a CH group. R ₁₉ and R ₂₀ may be the same or different and each represents a hydrogen atom or a group of an alkyl group having 1 to 4 carbon atoms, which is a CN-group, an OH-group or an NH ₂ group. Can be replaced by one of
It can be optionally substituted with one of the groups forming a heterocyclic group containing oxygen or nitrogen together with the carbon atom of the benzene ring. These heterocyclic groups can be substituted with one or more alkyl groups having 1 to 4 carbon atoms or 4'-aminophenyl group.

R ₂₁ and R ₂₂ may be the same or different and are each a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine, a cyano group, an alkyl group having 1 to 4 carbon atoms. Group or acetyloxy group. X represents an anion, preferably selected from hydrochloric acid, methyl sulfate and acetic acid. A is the following A1-A19
Represents a group selected from the structure of

[0102]

Embedded image

[0103]

Embedded image

Here, in the above formula, R ₂₂ has 1 to 4 carbon atoms.
And can be substituted with a hydroxyl group. R ₂₃ represents an alkoxy group having 1 to 4 carbon atoms.

[0105]

Embedded image

Here, in the above formula, R_{twenty four}Is a hydrogen atom
Represents an alkyl group having 1 to 4 carbon atoms. R_{twenty five}Is a hydrogen source
Alkyl group which can be substituted by a substituent, CN- group or amino group
Or a 4'-aminophenyl group;_{twenty five}
Is R_{twenty four}Together with an alkyl group having 1 to 4 carbon atoms
Represents a heterocyclic group optionally containing oxygen and / or nitrogen.
R ₂₆And R₂₇May be the same or different,
Such as hydrogen, bromine, chlorine, iodine or fluorine
Halogen atom, alkyl group having 1 to 4 carbon atoms, 1 to 1 carbon atom
4 represents an alkoxy group or a CN- group. X is negative
And preferably in hydrochloric acid, methylsulfuric acid and acetic acid
Choose from

[0107]

Embedded image

Here, in the above formula, R ₂₈ represents an alkyl group having 1 to 4 carbon atoms, and R ₂₉ and R ₃₀ may be the same or different, and are each a hydrogen atom or a carbon atom having 1 to 4 carbon atoms.
4 represents an alkyl group.

[0109]

Embedded image

In the above formula, R ₃₁ represents a hydrogen atom, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom such as bromine, chlorine, iodine or fluorine, or an amino group. R ₃₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ₃₂ forms a heterocyclic ring with a carbon atom of a benzene ring, which optionally contains an oxygen atom, and / or has one or more carbon atoms. It can be substituted with 1-4 alkyl groups. R ₃₃ represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine. R ₃₄
And R ₃₅ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. D ₁
And D _2, which may be the same or different and represent a nitrogen atom or a CH- group. m is 0 or 1. Therefore, R ₃₁ represents an unsubstituted amino group, and m is 0 when D ₁ and D ₂ are both CH- groups. X represents an anion, preferably selected from hydrochloric acid, methyl sulfate and acetic acid.

[0111]

Embedded image

In the above formula, R ₃₆ represents an alkyl group having 1 to 4 carbon atoms. When m is 0 and D ₁ represents a nitrogen atom, E also represents a group having the following structure E9. .

[0113]

Embedded image Here, in the above formula, R ₃₆ represents an alkyl group having 1 to 4 carbon atoms.

The above-mentioned general formulas (V) and (V) listed as the cationic direct dyes which can be added to the hair dye composition of the present invention.
The compounds represented by I), (VII) and (VII ') are described, for example, in patent application WO95 / 01772, WO95 /
15144 and known compounds as described in EP-A-0 714 954.

As the compound represented by the above general formula (V) listed as the cationic direct dye which can be added to the hair dye composition of the present invention, more specifically, the following structural formula (V1)
To (V52).

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

Among the above-mentioned compounds represented by the above-mentioned structural formulas (V1) to (V52), the above-mentioned structural formulas (V1) and (V52)
Compounds represented by 2), (V4), (V14) and (V31) are particularly preferred.

The compounds represented by the above general formula (VI) listed as the cationic direct dyes that can be added to the hair dye composition of the present invention, more specifically, the following structural formulas (VI1) to (VI12) The compound shown by these can be mentioned.

[0127]

Embedded image

[0128]

Embedded image

As the compound represented by the general formula (VII) mentioned as the cationic direct dye which can be added to the hair dye composition of the present invention, more specifically, the following structural formula (VI)
Compounds represented by I1) to (VII18) can be mentioned.

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

The structural formulas (VII1) to (VII1)
Among the above-mentioned compounds represented by 8), the above-mentioned structural formula (V
Compounds represented by II4), (VII5) and (VII13) are particularly preferred.

As the compound represented by the above general formula (VII ') as a cationic direct dye which can be incorporated into the hair dye composition of the present invention, more specifically, the following structural formula (V)
Compounds represented by II′1) to (VII′13) can be mentioned.

[0135]

Embedded image

The cationic direct dye or dye is used in an amount of about 0.001 to the whole hair dye composition of the present invention.
It is preferable that the amount is about 10% to about 10%, and it is particularly preferable that the amount is about 0.05% to about 5%.

In general, the acid addition salts suitable in the range of the hair dye composition based on the invention (oxidizing base compound and coupling agent) include hydrochloride, bromate, sulfate, tartrate and lactate. And acetate.

The laccase of the oxidase used in the present invention is not particularly limited in its origin and the like, but is preferably a microorganism-derived laccase, and particularly preferably a laccase derived from the genus Myceliophthora or the genus Citalidium. preferable. The amount of the laccase used in the present invention in the composition includes the form of the preparation, the frequency of use, the treatment time,
Although it depends on the titer of the enzyme preparation, it is usually 0.0005 to 20.
%, Preferably 0.005 to 10%.
If it is less than 0.0005%, a sufficient effect cannot be obtained.
Even if the amount is more than 0%, the effect corresponding to the increase in the added amount is not increased.

Here, the laccase is described in more detail. The term “laccase” is used in the enzyme classification E. coli. C. 1.10.3.2 (laccase). Laccase contains multiple copper,
Acts as a catalyst for oxidation reactions on phenols and aromatic amines. Laccase-mediated oxidation produces an allyloxy radical intermediate from the appropriate phenolic substrate,
The final binding of the resulting intermediate provides a dimer, oligomer or polymer reaction product.

As the laccase, for example, those derived from fungi, bacteria, or plants can be used. Among them, laccase derived from fungi is preferred. Among them, strains of the genus Ebrico sp. pin
situs or P.S. versicolor strains, such as M. Mycel like thermophila
Rhizocton, a strain belonging to the species iophthora
ia species are preferred, especially Rh. prati
cola or Rh. Solani strain, Pyric
ularia strains are more preferred, especially P. ory
zae or S.T. More preferred are Scytalidium strains such as thermophilium. Laccases are also used in plants such as the genus Rhus, for example, Rhus.
vernicifera.

The hair dye composition of the present invention comprises oxidoreductases such as laccase of Everyco species, especially WO96 /
Polyporus pinisit (from Novo Nordisk Vitec)
us laccase (also called Trametes vilosa laccase) or Myceliophth
ora laccase, especially described in WO 95/33836 (from Novo Nordisk Vitec)
Myceliophthora thermophil
Laccases such as a laccase can also be used.

Further, WO95 / 33837 and WO97
/ 19998 (from Novo Nordisk Vitec)
Described in S. Scytalidium such as thermophilium, or Sigma N
o. Pyricularia oryzae laccase, which can be purchased from Sigma as L5510, or C.I. Cop like cinereus laccase
laccase of the species Rinus, in particular C. cinereus
IFO 30116 laccase, or Rh. sol
laccases of the species Rhizoctonia such as ani laccase, in particular 6.0 to 8.5 as described in WO 95/07988 (from Novo Nordisk A / S).
Neutral Rh. Having an optimum pH range. solani laccase can also be suitably used.

The laccase of the present invention includes Colly
via, Forms, Lentinus, Pleuro
tus, Aspergillus, Neurospor
a, Podospora, e.g. radiata
Phlebia such as (WO92 / 01046), e.g. hirsitus (JP2-238885)
Species such as Coriolus, or Botryti
Those derived from fungi such as s can also be used.

In the present invention, in addition to the above laccase,
Further, a laccase-related enzyme can be blended. In this case, the “laccase-related enzyme” is referred to as the enzyme classification E. coli. C.
Catechol oxidase enzyme composed of 1.10.3.1, enzyme classification C. Bilirubin oxidase enzyme composed of 1.3.3.5 and E. coli. C. 1.14.9
Mono-phenol mono-oxygenase composed of 9.1. Bilirubin oxidase is preferably M. Myrothe like verrucaria
It is better to derive from a strain of Cium species. Peroxide (H
Oxidases producing ₂ O ₂ ) are generally used in combination with peroxidases to eliminate or at least reduce the peroxides produced. Suitable oxidases include glucose oxidase (EC 1.1.1.3.
4), hexose oxidase (EC.1.1.3.
5), L-amino acid oxidase (EC 1.4.
3.2), xylitol oxidase, galactose oxidase (EC 1.1.3.9), pyranose oxidase (EC 1.1.1.3.10) and alcohol oxidase (EC 1.1). 3.13).

When L-amino acid oxidase is blended into the hair dye composition of the present invention, Trichderma harmase is used as in L-amino acid oxidase described in WO 94/25574 (from Novo Nordisk A / S).
like zianum, or Trichoderm
Those derived from Trichoderma species, such as avride, can be used.

Preferred glucose oxidases include:
Aspergillus species such as Aspergillus niger, or Cladosporum species (Cladosp)
olium), especially Cladosporium oxy
and those originating from Sporum.

Red algae Chondrus crispus
(Commonly known as Irish moss) (S
ullivan and Ikawa, (1973), Bio.
chim. Biophys. Acts, 309, p.
11-22; Ikawa, (1982), Meth. i
n Enzymol. 89, Carbohydrate
metabolism Part D, 145-14
Hexose oxidase derived from 9) is D-glucose, D-galactose, maltose, cellobiose,
Lactose, D-glucose 6-phosphate, D-mannose, 2-deoxy-D-glucose, 2-deoxy-D
-Oxidizes a wide spectrum of carbohydrates such as galactose, D-fructose, D-glucuronic acid and D-xylose.

It is more preferable that the hair dye composition of the present invention further contains a weak reducing substance. Here, the weak reducing substance of the present invention refers to a pseudo-primary reaction which is an index of reducing ability. When the rate constant k _obs is measured by the following measurement method, it means a reducing agent having a value of 0.001 sec ^-1 or less.

<Method of Measuring Pseudo-First- _Order Reaction Rate Constant k _obs >
300 mM reducing agent, 100 phosphate buffer
Prepare a solution to make mM (pH = 5). Forensic dye No. 401 is added to this solution to a concentration of 0.2 mM, and the change with time of the peak at a wavelength of 575 nm is measured with a UV meter (UV-160 UV meter, Shimadzu Corporation). At this time, a rate constant of a change with time is obtained, and a pseudo first-order reaction rate constant k _obs is defined.

Specific examples of the above weakly reducing substances include, for example, sodium thiosulfate, dl-cysteine, N-acetyl-L-cysteine, thiourea, dithiodiglycolic acid, L-ascorbic acid, sorbic acid, adipic acid And salts thereof. The value of k _obs obtained by the above measurement method was 0.0081 for thioglycolic acid, which is a strongly reducing substance, and 0.1 for sodium sulfite.
On the other hand, sodium thiosulfate exemplified as the above-mentioned weakly reducing substance is 0.00075, N-acetyl-L-cysteine is 0.00031, and thiourea is 0.00045.

When the above-mentioned weak reducing substance is added to the hair dye composition of the present invention, the amount thereof is not particularly limited, and can be appropriately selected depending on the kind of the weak reducing substance. Usually, 10% or less, preferably 0.01 to 10%, more preferably 0.1 to 7% based on the whole composition.
It is preferable that If the amount is too large, the reducing action becomes too strong, and the hair dyeing properties may be suppressed. If the amount is too small, the effect of the compounding may not be sufficiently obtained.

The hair dye composition of the present invention may further comprise, if necessary, a pH buffer, a surfactant, a thickener such as hydroxyethylcellulose or xanthan gum, in addition to the above-mentioned components.
Flavors, preservatives, ultraviolet absorbers, antioxidants, bactericides, pearling agents and the like can be added. Here, as the surfactant, α-olefin sulfonate, alkane sulfonate, fatty acid alkyl ether carboxylate,
N- acylamino acid salt and C ₁₂ -C ₁₈ anionic surfactants such as saturated or unsaturated fatty acyl glutamic acid esters, alkyl betaines, alkylamido betaines, amphoteric surfactants such as sulfobetaine, quaternary ammonium mono- or dialkyl Any of a cationic surfactant such as a salt and a nonionic surfactant such as a polyoxyethylene alkyl ether and a fatty acid alkylolamide can be used.

In order to improve the feel of the hair, silicone derivatives such as dimethylpolysiloxane, amino-modified silicone and polyether-modified silicone can be blended.

The hair dye composition of the present invention can be prepared in any form such as liquid, cream, gel, aerosol, etc. In this case, it is prepared in one form from the viewpoint of usability and the like. Is preferred.

When the above components are blended to prepare a composition, the blending is preferably performed in a vacuum or in an atmosphere of an inert gas such as nitrogen gas, carbon dioxide gas, or a rare gas. The compounding method may be any method, and is not particularly limited. For example, there is a method of performing vacuum vacuum, replacing with nitrogen gas, or performing vacuum vacuum and then replacing with an inert gas.

The composition of the present invention is particularly preferably in the form of an aerosol. When the composition is in the form of an aerosol, it is preferable to add a shaking operation during and / or immediately after filling the propellant. This is an operation for forcibly consuming the residual oxygen in the container and suppressing the generation of the dye precursor.
That is, the dye does not insolubilize or agglomerate in the system, thereby improving the stability. The method of shaking may be any method such as vertical shaking, horizontal shaking, turning shaking, and figure eight shaking, and is not particularly limited. The shaking time is 10 seconds to 30 minutes, preferably 1 to 10 minutes, depending on the type.

The propellant was liquefied propane gas (LP
G), dimethyl ether (DME), nitrogen gas, carbon dioxide gas or the like may be used.
Is good.

Although the propellant can be filled under air, it is more preferable to use a vacuum or an inert gas atmosphere such as a nitrogen gas, a carbon dioxide gas, or a rare gas. , Is not particularly limited.

The hair dye composition of the present invention has a pH of 5.0 to 5.0.
9.5 is preferred, and more preferably 6.0 to 8.0. If the pH is greater than 9.5, irritation may be a problem.

[0160]

EXAMPLES The present invention will be described below in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples,% indicates% by weight. The performance test methods used in the following examples are as follows.

Skin irritation: The method of Kimber et al. (Toxico) used as an animal alternative to assess sensitization
l. Lett. 55: 203-213, 1991), the method of Hostinec et al. (Arch. Dermatol.
Res. 287: 567-571, 1995). That is, the color developing substance was dissolved in an acetone: olive oil mixed solution (mixing ratio: 4: 1) so as to be 2%, and these solutions were applied to the back skin of an 8-week-old Balb / c mouse. Lymph nodes were removed from the mice treated on day 5 after application, and lymphoid cells were PRM containing autologous serum.
The cells were suspended in an I1640 medium to prepare a lymphoid cell liquid.
The obtained lymphoid cells were cultured at 37 ° C. in the presence of 5% CO ₂ for 3 hours.
After culturing for a day, the proliferation activity of the culture solution was measured. The degree of sensitization was determined by calculating the sensitization index by the following formula and comparing it with the following criteria.

[0162]

(Equation 1)

Hair dyeing property (ΔE): About 10 g of a hair bundle of dry goat gray hair is shampooed, drained (the weight of the hair bundle after draining the water is 17 g), and 3 g of each of the following compositions is quickly added thereto. It was applied uniformly. It was left at 30 ° C. for a certain time and rinsed. After drying, it was shampooed and air-dried, and the hair dyeing properties of goat hair were evaluated. The hair dyeing property (ΔE) is measured by measuring the L, a, and b values of the dyed hair bundle with a color difference meter (SE2000 manufactured by Nippon Denshoku Co., Ltd.), and the color difference (ΔE) from the undyed hair is determined to evaluate the hair dyeing property. did. Note that ΔE indicates that the larger the value, the better the hair dyeing property.

[Examples and Comparative Examples] A one-pack hair dye composition having the following formulation was prepared and its performance was evaluated. Table 2 shows the results.

Example 1 (Gel Type) Blending Component Blending Amount (%) 5,6-dihydroxyindoline / HBr 3 Laccase (genus Myceliophthora) 0.5 Xanthan gum 0.5 Hydroxyethylcellulose 0.5 Ethanol 5.0 Purified water Balance Total 100.0 (pH (NaOH adjustment) 7.0)

Example 2 (Gel Type) Ingredients Amount (%) 5,6-dihydroxyindoline / HBr 2 Toluene-2,5-diamine sulfate 0.01 Paraaminophenol 0.01 Laccase (genus Scytalidium) 0.5 Xanthan gum 0.5 Hydroxyethyl cellulose 0.5 Ethanol 5.0 Purified water Balance meter 100.0 (pH (NaOH adjustment) 7.0)

Comparative Example 1 (Gel Type) Ingredients Ingredients (%) Toluene-2,5-diamine sulfate 3 Paraaminophenol 1 Laccase (Genus Myceliophthora) 0.5 Xanthan gum 0.5 Hydroxyethylcellulose 0.5 Ethanol 5.0 Purified water balance meter 100.0 (pH (NaOH adjustment) 7.0)

Example 3 (Cream type) Ingredients Ingredients (%) 5,6-dihydroxyindoline / HBr 3 Decaglyceryl monostearate 3 Cetostearyl alcohol 0.5 Stearic acid 0.8 Xanthan gum 1 Laccase (genus Myceliophthora) 1 Carboxymethylcellulose 1 Sodium hydroxide Appropriate amount Purified water Balance meter 100.0 (pH (NaOH adjustment) 7.0)

Example 4 (Cream type) Ingredients Ingredients (%) 5,6-dihydroxyindoline / HBr 3 POE (10) cetyl ether 8 stearyl alcohol 2.5 oleyl alcohol 5 behenyl alcohol 2 cetyl alcohol 2 stearyl trimethylammonium chloride Reference Signs List 1 laccase (derived from urushi) 1 glycerin 2 triethanolamine appropriate amount purified water Balance meter 100.0 (pH (NaOH adjustment) 7.0)

Comparative Example 2 (Cream type) Ingredients (%) Toluene-2,5-diamine sulfate 3 paraaminophenol 1 decaglyceryl monostearate 3 cetostearyl alcohol 0.5 stearic acid 0.8 xanthan gum 1 laccase ( Myceliophthora) 1 Carboxymethylcellulose 1 Sodium hydroxide Appropriate amount Purified water Balance meter 100.0 (pH (NaOH adjustment) 7.0)

[0171]

[Table 1]

[0172]

[Table 2]

Further, a one-part hair dye composition having the formulation shown in Table 3 was prepared, and its performance was evaluated. Table 4 shows the results.

[0174]

[Table 3]

[0175]

[Table 4]

[0176]

The hair dye composition of the present invention has less skin irritation and has an excellent hair dyeing effect.

Claims (3)

[Claims] 1. A hair dye composition comprising an indoline and / or an indoline compound and a laccase. 2. The method according to claim 1, further comprising a weakly reducing substance.
The hair dye composition according to the above. 3. The hair dye composition according to claim 1, which is a one-pack type.